Reaction product of aldehydes and triazine derivatives



Patented Jan. 4,1944

UNITED STATES PATENT OFFICE amass aasc'rros raonuc'r or mamas armrarszma pamvs'rrvas Gaetano F. D'Aieiio and James W.

Pittsiieid, Mara,

Underwood.

minors to General Electric Company, a corporation of New York- NoDrawing. Application September 12, 1942,

Serial No. 458,180

20 Claims.

This invention relates to the production of new synthetic materials andespecially to new reaction products having particular utility in theplastics and coating arts. Specifically the invention is concerned-withcompositions of matter comprising a condensation product of ingredientscomprising an aldehyde, including polymeric aldehydes, hydroxyaldehydesand aldehyde-addition products, e. g., formaldehyde, paraformaldehyde,dimethylol urea, trimethylol melamine, aldol, glycollic aldehyde, etc,and a poly-(triazinyl phenylpropyl. etc.) and-their homologues, as wellhydrazino) derivative of 'a polycarboxylic acid corresponding to thegeneral formula:

1 NHR BEN- e-NH- NH- In the above formuliR represents a member of asthose groups with one or more of their hydrogen atoms substituted by,for example, a halogen, more particularly chlorine, bromine, fluorine oriodine. Specific examples of halogeno-substitilted hydrocarbon radicalsthat R inthe above formula may represent are: chloromethyl, chloroethyl,chlorophenyl, diohlorophenyl, ethyl chlorochlorocyclohexyl, phenylchloroethyl, bromoethyl, bromopropyl, iodcphenyl, fluorophenyl.bromotolyL-etc. Preferably R in Formula I is hydrogen, in which case thecompounds may be represented by the general formula:

u I NH| where n and if have the same meanings as given above withreference to Formula I,

and n represents an integer having a value equal to the valency of thepolyacyl radical 01 Y. Insteadoi' the symmetrical triazine (s-trlazine)derivatives represented by the above formula, corresponding derivatives-of the asymmetrical tri azines or of the vicinal triazines may beemployed.

This application is a continuation-in-part of our copending applicationSerial No. 455,811,!ied August 22, 1942, and assigned to the sameassignee as the present invention.

Illustrative examples of radicals that R in the above formula mayrepresent are: aliphatic (e. g.,

methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, isobutyl,butenyl, amyl, isoamylfhe'xyl, octyl, allyl, methallyl, ethallyl,crotyl, etc.), in-

- cluding cycloaliphatic (e. g., cyclopentyl, cyclopentenyl, cyciohexyl,cyclohexenyl, cycloheptyl,

etc): aryl (e. g., phenyl, diphenyl or xenyl, naphv 5 thyl, anthracyl,etc); aliphatic-substituted aryl e. g., tolyi, xylyl, ethylphenyl,propylphenyLiso-Q propylphenyl, allylphenyl', Z-butenylphenyl,tertirary-butylphenyl, etc); aryl-substituted aliphatic (e. g., benzyl,phenylethyl, cinnamyl,

Illustrative examples of polyacyl radicals that Y in Formulas I and 11may represent are: allphatic polyacyl (e. g., oxalyl, malonyl, succinyl,glutaryl, adipyl, tricarballylyl, etc.), including unsaturated aliphaticpolyacyl (e. g., maleyl,..

tumaryl, glutaconyl, itaconyl, citraconyl, mesaconyl, glutinyl,aconityl, muconyl, etc); and aromatic polyacyl, e. g., phthalyl,naphthalyl, trimesyl, chlorophthalyl, bromophthalyl, isophthalyl,terephthalyl, etc. Preferably Y is a succinyl or a phthalyl radical.

The poly-(triazinyl hydrazino) derivatives of polycarboxylic acids thatare used in carrying the present invention into eiiect are more fullydescribed and are specifically claimedin our parent'copendingapplication Serial No. 455,811. As pointed out in this copendingapplication, a

7 method of preparing the triazine derivatives used in practicing thepresent invention comprises efl'ecting reaction in the presence 01' ahydrohalide acceptor, e. g.-, a tertiary amine such as a trialkyl or atriaryl amine. between 1) a triazine derivative corresponding to thegeneral formula NHR N N arm- CII-NHNHQ i N and '(2) an acyl halidecorresponding to the gen-- 5 eral formula Yx, where X represents ahalogen atom, and n, Y and B have the same meanings as given above withreference to Formula I, each halogen atom represented by X being linkeddirectiy to a carbon atom of a carbonyl group'of the polyacyl radicalrepresented by Y. a

- Bls-(diamino Bisdi- (bromo anilinol Examples of compounds embraced byFormula I that may be used in producing our new con densation productsare listed below: Alpha,beta-bis-(diamino s-triazinyl hydrazinecarbonyl)ethane Bis-(diamino s-triazinyl hydrazinocarbonyl)Alpha,beta-bis-[di-(methylamino) carbonyl] ethane.Alpha,beta;gamma-trl'- (diamino. s-triazinyl hydrazinocarbonyl) propaneBis-(diamino s-triazinyl hydrazinocarbonyl) benzenesBis-[di-(methylamino) carbonyl] methane Bis-(diamino s-triazinylhydrazinocarbonyl) methane Alpha,omega-bis-(diamino s-triazinyl hydrazinocarbonyl) butane I 4 A1pha,beta-bis-[di-(ethylamino) s-triazinylhydrazinocarbonyll. ethane ls-triaainyl hydrazino hydrazino-Bis-(dianilino s triazinyl hydrazlnocarbonyl) methane carbonyl] methaneAlpha,beta-bis-(diamino s-triazinyl hydrazine- Bis-(4-anilino G-aminos-triazinyl-2 hydrazinocarbonyl) methane Bis-[di-(isobutylamino)s-triazinyl hydrazinos-triazinyl hydrazino- Bis-(4-methylamino, 6-aminos-triazinyl-2 hydrazinocarbonyl) Bis-(4-anilino B-methylaminos-triazinyl-2 hydrazinocarbonyl) benzene Bis-(ditoluidb s-triazinylhydrazinocarbonyl) benzenes 4 Alpha,beta-bis-(dikylidino s-triazinylhydrazinecarbonyl) ethane 'Alpha,beta bis [di (phenethylamino)s-triazinyl hydrazinocarbonyll 'ethane Bis-[di-(ethylanilino)s-tria'zinyl 'hydrazinocarbonyll benzenes 1,3,5 tri (diamino s triazinylhydrazinocarbonyl) benzene s-triazinyl hydrazinocarbonyl) bromobenzenesBis-[di-(chloromethylamino) s-triazinyl hydrazinocarbonyll s-triazinylhydrazinecarbonyl] methane Bis-[di-(allylamino) s-triazinylhydrazinocarbonyll methane Bis-[di-(cyclohexylamino) s-triazinylhydrazinocarbonyl] ethanes Bis-[di-(octylamino) s-triazinylhydrazlnocarbonyll propanes Bis-[di-(iodotoluido) s-triazinylhydrazin'ocarbonyll isopentanes Bis-(diamino s -triazinylhydrazinocarbonyl) chloropropanes Bis-[di-(bromoanilino) carbonyl]heptanes Bis-[di-(chlorotoluido) s-triazinyl hydrazinocarbonyl] benzeness-triazinyl hydrazino- Bis- [di- (fluoroanilino) s-triazinylhydrazinocarbonyl] butanes I Bis-[di-(cyclohexenylannno) .s-triazinylhydrazinocarbonyl] naphthalenes 'Bis-[di-(pentylamino) -s-triazinylhydrazinocarbonyl] chlor'onaphthalenes Bis-[di-(xenylamino) s-triazinylhydrazinocarbonyll xylenes Bis-[di-(naphthylamlno) s-triazinylhydrazinecarbonyll ethylbenzenes Bis-[di-(chloroethylamino) s-triazinylhydra- -zinocarbonyll toluenes Bis-[di- (butylaminoi s-triazinylhydrazinocari bonyll propanes Bis-[di-(bromopropylamino) s-triazinylhydrazinocarbonyll' butanes Alpha,beta-bis- [di- (propenylamino)hydrazinocarbonyl] propane Bis-(diamino s triazinyl hydrazinocarbonyl)toluenes I Bis-(diamino s-triazinyl lrvdrazinocarbonyl)" xy,-

lenes Bis-(dianilino s-triazinyl hydrazinocarbonyD V ethanesBis-(ditoluido ethanes It will be noted that the above list of compoundsembraced by- Formula I includes both poly-(diamino s-triazinylhydrazinocarbonyD- substituted aliphatic hydrocarbons, more particularlybis-(diamino s-triazinyl hydrazinocars-triazinyl hydrazinocarbonyl)bonyl) alkanes and alkenes, and poly-(dlamino s-triazinyl,hydrazinocarbonyl) -substituted aromatic hydrocarbons.

The present invention is based on our discovery that new and valuablematerials having particular utility in the plastics and coating arts canbe produced by effecting reaction between .ingredients comprisingessentially an aldehyde, including polymeric aldehydes, hy-

' droxyaldehydes and aldehyde-ariditiom products.

and a triazine derivative of the kind embraced by Formula],- numerousexamples of which have been given above and in our parent copendingapplication Serial No. 455,811. Due to the numerous reactive, positionsin the triazine derivatives employed in practicing our invention, curedresinous aldehyde-reaction products prepared therefrom are outstandingin their resistance to water and organic solvents. The gloss and generalappearance of molded articles made from ,molding compounds containingthese new resins inheat-conv'ertible state also are exceptionally good.Othe'r improved properties, including improved plasticity combined withrapid-curing characteristics and, also, high resistance to heat andabrasion-.111, the cured state, make the prodnets of the presentinvention suitable for main fields of utility, for instance inelectrically insulatingapplications, for which resinous materials ctiesser resistance to heat, water, abrasion and organic solvents would bewholly unsuited.

It has been known heretofore that resinous materials can be prepared byeffecting reaction between an aldehyde and certain aminotriazines.

e.' g., melamine, ammeline and thioammeline ethers. While such resinsare suitable for numerous industrial applications, they are not entirelysatisfactory for some uses where optimum heat-; waterandabrasion-resistance are required. Furthermore, in some cases theircuring characteristics and plastic flow during molding are inadequatefor the high-speed molding techniquerequired for economical and emcientmolding operations? These and other production s-triazinyl dimeultiesand deficiencies in useful properties of the resin are obviated bycreating a synthetic composition from ingredients comprising essentiallyan aldehyde and a triazine derivative of the kind embraced by Formula I.In practicing our invention the initial condensation reaction may becarried out at normal copending applications of one or both or us, for

or at elevated temperatures, at atmospheric,

sub-atmospheric or super-atmospheric pressures, and under neutral,alkaline or acid conditions. Preferably the reaction between thecomponents 'is initiated under alkaline conditions.

. line or acid conditions for the initial condensation reaction. Forexample, we may use an alkaline substance such as sodium, potassium orcalcium hydroxides, sodium or potassium car-, I

bonates, mon6-, dior tri-amines, etc. In some cases it is oftendesirable to cause the initial to take placein the presence of a primarycondensation catalyst and a secondary condensation catalyst. The primarycatalyst advantageously is either an aldehyde-non-reactablenitrogen-containing basic tertiary compound, e. g., tertiary amines suchas trialkyl (e. g., trimethyl, triethyl, etc.) amines, triaryl-(e. g.,triphenyl, tritolyi, etc.) amines, etc., or an aidehyde-reactablenitrogen-containing basic compound, for instance ammonia, primary amines(e. g., ethyl amine, propyl amine, etc.) and secondary amines (e. g.,diprppyl amine, dibutyl amine-etc.). The secondary condensationcatalyst, which ordinarily is used in an amount less than the amount ofthe primary catalyst, advantageously is a fixed alkali, for instance acarbonate, cyanide or hydroxide of an alkali metal (e. g., sodium,potassium, lithium, etc.).

Illustrative examples of acid condensation catalysts that may beemployed are inorganic or organic acids such as hydrochloric, sulfuric,phosphoric, acetic, lactic, acrylic, malonic, etc., or acid salts suchas sodium acid sulfate, monosodium phosphate, monosodium phthalate, etc.Mixtures of acids, of acid salts or of acids and of acid salts may beemployed if desired. The reaction between the aldehyde, e. g.,tormaldehyde, and the triazine derivative may be carried out in thepresence or absence of solvents or diluents, other natural or syntheticresinous bodies, or while admixed with other materials that also canreact with the aldehydicj reactant or with the triazine derivative, e.g., urea (NHzCONHz), thiourea, selenourea, iminourca (guanidine),substituted ureas, thioureas, selenoureas and lminoureas, e. g.,aldehyde-reactable urea derivatives such as mentioned in DAleio PatentNo. 2,285,418, issued June 9,

1942, page 1, column 1, lines 40-49; monoamides oi monocarboxylic andpolycarboxylic acids and polyamides of polycarboxylic acids, e. g.,acetamide, halogenated acetamides (e. g., a chlorinated acetamide),maleic monoamide, malonic monoamide, phthalic monoamide, maleic diamide,tumaric diamide, malonic diamide, itaconic diamide, succinic diamide,phthalic diamide, the monoamide,'diamide and triamide of tricarballylicacid, etc.; 2,4,8-triaminopyrimidine, etc.; aldehyde-reactable triazinesother than the trlazine derivatives constituting the primary componentsoi the resammeline, ammelide, melem, melam, melon, numerous otherexamples being given in various instance in D'Alelio copendingapplication 8erial No. 377,524, filed February 5, 1941, and inapplications referred to in said copending application; phenol andsubstituted phenols, e. g., the cresols. the xylenols, the tertiaryalkyl phenols and other phenols such as mentioned, for example, inD'Alelio Patent No; 2,239,441, issued April 22, 1941; monohydric andpolyhydric alcohols, e. g., butyl alcohol, amyl alcohol, heptyl alcohol,octyl alcohol, '2-ethylbutyl alcohol, ethylene glycol, propylene glycol,glycerine, polyvinyl alcohol, etc.; amines, including aromatic amines,e. g., aniline, etc.;' and the like.

,The modifying reactants may be incorporated with the triazinederivative and the aldehyde to form an intercondensation product bymixing all the reactants and eiiecting condensation therebetween or byvarious permutations of reactants as described, for example, in DAlelioPatent No. condensation reaction between the components 2,281,559,issued May 5, 1942 (page 2. column 1,

lines 48-69), with particular reference to reactions involving anon-haloacylated urea, a halogenated acylated urea'and an aliphaticaldehyde.

:5 For instance, we may form a partial condensation product oringredlentscomprlsing 1) urea or melamineor urea and melamine, (2) atriazine derivative of the kind embraced by Formula I, for examplebls-(diamino s-triazinyl hydrazinocarbonyl) ,a poly-(diamino s-trlazinylhydrazinecarbonyl) substituted aliphatic hydrocarbon, more particularlya bis-(diamlno s-triazinyl hydrazinocarbonyl)-substituted alkane such,for

instance, as alpha, beta-bis-(diamino s-triazinyl hydrazinocarbonyl)ethane, etc., a poly-(diamino s-triazinyl hydrazinocarbonyl)-substitutedaromatic hydrocarbon, e. g., a bis-(diamino s-triazlnylhydrazinocarbonyli benzene, etc., and (3) an aldehyde, includingpolymeric aldehydes, hy-

droxyaldehydesand aldehyde-addition products,

ifor instance .iormaldehyde, paraiormaldehyde,

glyceraldehyde, dimethylol urea, a polymethylol melamine, e. g.,hexamethylol melamine, etc. Thereafter we may efl'ect reaction betweenthis partial condensation product and, for example,

aminodiazines, e. g.,

ins oi the present invention, e. g., melamine,

a curing reactant, specifically a chlorinated acetamide, to obtain aheat-curable composition.

Some oi the condensation products of this invention are thermoplasticmaterials even at an advanced stage of condensation. while others arethermosetting or potentially thermosetting bodies that convert underheat or under heat and pressure to an insoluble, ini'usible state. The

The liquid intermediate condensation products of the invention may beconcentrated or diluted iurther by the removal or addition 01' volatilevsolvents to form liquid coating compositions or adjusted viscosity andconcentration. The heatconvertible or potentially heat-convertibleresinous condensation products may be used in liquid state, for instanceas'suriace-coating materials, in the production oi'paints, varnishes,lacquers, enamels, etc., for general adhesive applications, in producinglaminated articles and for numerous other purposes. The liquidheat-harden'able or potentially heat-hardenable condensation productsmay be used directly as'casti ng resins, ,while Alpha, beta-bis-(diaminos-triazinyl hythose which are of a gel-like nature in partiallycondensed state may be dried and granulated to form clear, unfilledheat-convertible resins.

In order that those skilled in the art better may understand how thepresent invention may be carried into effect, the following examples aregiven by way of illustration and not by way of limitation. All parts areby weight.

Example 1 drazinocarbonyl) ethane; which also may be named succinylbis-(diamino s-triazinyl hydrazide) Aqueous formaldehyde (approx. 37.1%

HCHO) n, 194.4 Aqueous ammonia (approx. 28% NH':) 15.0 Sodium hydroxidein 10 parts water 0.2 'Chloroacetamide (monochloroacetamideL 1.0

All of the above ingredients with the exception of th chloroacetamidewereheated together under reflux at the boiling temperature of the massfor 15 minutes, yieldinga clear, colorless syrup.

Whena small sample of this syrup was heated on a 140 C. hot plate, itcured slowly to an infusible state. The chloroacetamide was added to themain batch of the syrupy condensation product and refluxing wascontinued for an additional minutes. The resulting chloroacetamidemodified syrupy resin cured more, rapidly than the unmodified syrup toan insoluble and infusible state when a small sample of it was heated ona 140 C. hot plate,

The chloroacetamide-imodifled syrup'was di-.

vided into. two equal portions. Theone portion was mixed with 40 partsalpha cellulose in flock form and 0.2 part of a mold lubricant,specifically zinc stearate, to form a molding (moldable) composition ofthe cellulose-filled type. The wetmolding compound was dried to 65 C.for 1 hour. A sample of the dried and ground molding compound was moldedfor 4 minutes at 130 C. under a pressure of 2,000 pounds per squareinch. The molded: piece was well cured throughout, was extremely hardand had a smooth, glossy surface finish. It had outstanding resistanceto water as shown by the fact that it absorbed only 0.25% by weight ofwater when immersed in boiling water for 15 minutes, followed byimmersion in cold water for 5 minutes. The molded article showed noevidence of being attacked by this rigid test. The molding compound hadgood plastic flow during molding.

An asbestos-filled molding compoundwas made rat-ts.

active curing catalysts (e. g., citric acid, phthalic anhydride, malonicacid, oxalic acid, etc.),

- orlatent curing catalysts (e. g., sodium chlorofrom the other half ofthe chloroacetamide-modi- I fled syrup by mixing therewith 100 partsasbestos and 0.2 part of zinc stearate. The wet molding composition wasdried for 2 hours at 64 C. A

well-cured molded piece having a good surface appearance and very goodresistance to water was obtained by molding a sample of the dried andground molding compound for 5 minutes at 130 C. under a pressure of2,000 pounds per square inch. When tested for its water resistance asabove described, the molded piece absorbed only 1.19% by weight ofwater. composition exhibited good plasticity during molding as evidencedby the-amount of flash on the molded piece.

Instead of using chloroacetamide in accelerating the curing of thepotentially reactive resinous material heat-convertible compositions maybe produced by adding to the partial condensation product'iin syrupy orother form) direct or The moldingacetate, N-diethyl chloroacetamide,glycine ethyl ester-hydrochloride, etc.), or by'intercondensation withcuring reactants other than monochloroacetamide (e. g., 111- andtri-chloroacetamides,

chloroacetonitriles alpha,beta-dibromopropionitrile, ethylene diaminehydrochloride, aminoacetamide hydrochloride, the ethanolaminehydrochlorides, nitrourea, chloroacetyl 'urea, glycine,

chloroacetone, sulfamic acid, citric diamide, f I

phenacyl chloride, etc.) Other examples of ouring reactants that may beemployed to accelerate or to effect the curing of'the thermosetting orpotentially thermosetting resins of this and other examples are given invarious co'pending applications of one or both of us... for instance inDAlelio copending applications Serial No. 346,962, filed July 23, 1940,now Patent 2,325,375, and Serial No. 354,395, filed August 27, 1940,-now Patent No. 2,325,376, both of which applications issued on July 27,1943, and are assigned to the same assignee as the present invention.

EmmpleZ Parts Alpha, beta-bis-(diamino is-triazinyl hydrazinocarbonyl)ethane 43.7 Urea 28.8 Aqueous formaldehyde (approx. 37.1%

HCHO) p 97.2 Aqueousammonia (approx.- 28% NH:).. 1.5 Sodium hydroxide in5 parts water 0.1 Chloroacetamide, -1 0.5

All of the above ingredients with the exception of thechloroacetamidewere heated together under reflux atthe boilingtemperature of the mass for 20 minutes. The chloroacetamide was nowadded and heating under reflux was continued for an additional 8minutes. A molding compound was made from the resulting resinous syrupby mixing therewith 40 parts alpha cellulose and 0.2 part zinc stearate.The wet molding composition was dried for 1% hours at 65 C.

A well-cured molded article was obtained by molding a sample of thedried and ground mold ing compound for 5 minutes at C. under a pressureof 2,000 pounds per square inch. The

All of the above ingredients with the exception of the chloroacetamidewere heated together-under reflux at the boiling temperature of the massfor 10 minutes after which the chlpracetamide was added and refluxingwas continued for an additional 5 minutes. The resulting resinous syrupwas mixed with 40 parts alpha cellulose and 02 part zinc stearate,yielding a molding composition which thereafter was-dried for 1 hour at65 C. A well-cured molded piece was obtained .by molding a sample of thedried and ground molding compound for 5 minutes at 130 C. under apressure of 2,000 pounds per square inch. The

molding composition showed good plastic now during molding.

All of the above ingredients with the exception of the chloracetamidewere heated together under reflux at the boiling temperature of the massfor 20 minutes. The chloroacetamide was now added and refluxing wascontinued for an additional minutes. A molding compound was preparedfrom the resulting resinous syrup by mixing therewith 60 parts alpha.cellulose and 0.4 part zinc stearate. The wet molding composition wasdried for 1 hours at 65 C. A wellcured molded piece having an excellentsurface appearance and good water resistance was obtained by molding asample of the dried and ground molding compound for 5 minutes at 130 C.under a pressure of 2,000 pounds per square inch. The molding compoundshowed good plastic flow during molding.

The dimethylol urea in the above formula may be replaced in whole or inpart by an equivalent amount of other aldehyde-addition products,

- e. g., a methylol melamine, more particularly a polymethyxlol melaminesuch, for instance, as trimethylol melamine, hexamethylol melamine, etc.7

Example 5 t Parts Alpha, beta-bis-(diamino s-triazinylhydrazinocarbonyl) ethane 109.2 Acrolein 100.8 Sodium hydroxide in 5parts water 0.1 Water 100.0

were heated together under reflux at the boiling temperature of the massfor minutes, yielding a yellow. resinous mass that cured to aninsoluble, infusible state inthe absence of an added curing agent when asmall sample .of it was heated on a 140 C. hot plate. The cured resinwas outstanding in its resistance to attack by organic solvents. Theresinous condensation product of this example is suitable for use in thepreparation of molding compositions.

Example 6 V Parts Alpha, beta-bis-(diamino s-triazinylhydrazinocarbonyl) ethane 109.2

mm alcohol 111.0

Aqueous formaldehyde (approx. 37.1%

, ECHO) Sodium hydroxide in 5 parts water s-- were heated together underreflux at the boilin: temperature ofthe massfor 15 minutes. yielding aclear, colorless sy py resin. This resin was potentially heat-curable asshown by the fact that when a .small'amount of chloros,sss,sss I n whichwas soluble in ethyl alcohol. The resin- 7 Example 7 Parts Alpha,beta-bis-(diamino s-triazinyl hydrazinocarbonyl) ethane 109.2 Acetarnide18.0

Aqueous formaldehyde (approx. 37.1%

HCHO) 145.8 Sodium hydroxide in 5 parts water 0.1

ous material of this example may be used in the preparation of variouscoating and impregnating compositions. It may be employed as a modifierof varnishes of the aminoplast and alkydresin types. a

were heated together under reflux at the boiling temperature of the massfor 15' minutes, yielding a clear, syrupy condensation product. Theresinous syrlip was potentially heat-curable ,as shown by the fact thatwhen citric acid,

chloroacetamide, phenacyl chloride or other curing agent such asmentioned under Example 1 was incorporated into samples of the syrup,the

individual sample cured to an insoluble, infusible I state upon heatingon a 140C. hot plate; The

I plasticity of the modified syrup during curing indicated that theproduct of this example would be suitable for'use as a modifier of lessplastic aminoplasts to improve their plasticity.

Example 8 I Parts Alpha, beta-bis-(diamino s-triazinylhydrazinocarbonyl) ethane 109.2 Glycerin .276

Aqueous formaldehyde (approx. 37.1%

HCHQ) Sodium hydroxide in 5 parts water 0.1

were heated together under reflux at boiling temperature for 15 minutes,yielding a thick, resinous syrup having curing characteristicsmuch thesame as the syrupy condensation product of Example'7. The resinousmaterial of this example may be used as a modifier of other syntheticresins or in the production of various coating and impregnatingcompositions.

Example 9 Alpha, beta-bis-(diamino s-triazinyl hydrasinocarbonyl) ethane109.2

.Diethyl malonate 48.0

Aqueous formaldehyde (apDrox. 37.1%

HCHO) 145.8 Sodium hydroxide in 5 parts water 0.1

were heated together under reflux at the boiling temperature of the massfor 10 minutes, yielding a gel which was rigid at room temperature; The

gelled resin melted and then cured to an inacetamide, glycine. suli'amicacid or other curing agent such as mentioned under Example 1 wasincorporated either into the syrupy condensation product or into thedehydrated resin, followed by heating on a 140 C. hot plate, thematerial cured to an infusible mass. A portion of the syrup wasconcentrated by evaporation to a thick resin HCHO) 145.8 Sodiumhydroxide 1115 parts water. 0-1

I Water soluble and 'infusible state when a small sample of it washeated on a 0. hot plate. The uncured resin was insoluble in solvents,specifically alcohols.

f Example 10 Alpha, beta-bis-(diamino s-triazinyl hydraainocarboayl)ethane 109.2 Polylvinyl alcohol {79.'2

Aqueous formaldehyde. (approx. 37.1%

Parts I water and organic Parts were heated together-under reflux atboiling tem- I perature for 20 minutes, yielding a very viscous syrupthat was converted into a tough, thermoplastic film when a smallsampleof it was heated on a 140 0. hot plate. The addition of an acid,specifically hydrochloric acid, to the syrup inan amount sufiicient tolower its pH to about 4.0 yielded a thermosetting resin that curedrapidly to an insoluble, infusible state when a small sample of it washeated on a 140 0. hot,

plate. The resinous material of this example may be used in theproduction of molding compositions or it may be employed in thepreparation of various liquid coating and impregnating Compositions.

It will be understood, of course, by those skilled in the art that thereaction between the aldehyde and the triazine derivative may beeffected at temperatures ranging, for example, from temperature to thefusion or boiling temperature of the mixed reactants, or of solutions ofthe mixed reactants, the -reaction proceeding more slowly at normaltemperatures-than at elevated temperatures in accordance with thegeneral law of chemical reactions. Thus, instead of effecting reactionbetween the ingredients of Examples 1 to 10, inclusive, under reflux atthe boiling temperature uf the mass as mentioned in the individualexamples, the reaction between the components may be carried out atlowertemperatures, for example at temperatures ranging from room temperatureto a temperature near the boiling temperature using longer reactionperiods and, in some cases, stronger catalysts and higher catalystconcentrations.

It also will be understood by those In producing these new condensationproducts the choice of the aldehyde is dependent largely upon economicconsiderations and upon the particular properties desired in thefinished product.

We prefer to use as the aldehydic reactantformaldehyde or compoundsengenderinz formaldehyde, e. 5., paraformaldehyde, hexamethyle'netetramine, etc. Illustrativeexamples of other aldehydesthat may be usedare acetaldehyde,

propionaldehyde, butyraldehyde, heptaldehyde, octaldehyde,metha'erolein, crotonaldehyde,

. benzaldehyde, furfural, hydroxyaldehydes (e. -g'.',

aldol, glucose, glycollic aldehyde, glyceraldehyde,

etc.), mixtures thereof, or mixtures of forma.d e-" hyde (or compoundsengenderlng formaldehyde) with such aldehydes. Illustrative examples ofaldehyde-addition products that may be used in-.

stead of the aldehydes themselves are themonoand poly-(N-carbinol)derivatives of urea, thlourea, selenourea and iminourea, and ofsubstituted ureas, thioureas, selenoureas and iminoureas, monoandpoly-(IN-carbinol) derivatives of amides of pclycarboxylic acids, e. g.,maleic, itaconic, fumaric, adipic, malonic, succinic, citric,

v skllledtin. the art that ourinventionis not limited to conphthalic,etc., monoand poly-(N-carbinol) derivatives of the aminodiazines, ofjthe aminotriazoles, etc. Particularly good results are obtained withactive methylene-containing bodies 5 such as a. methylol urea, moreparticularly monoand di-methylol ureas, and a methylol melamine, e. g.,monomethylol melamine and polymethylol 'melamines (di-, ,tri-, tetra-,pentaand hexamethylol melamines). Mixtures of aldehydes e. g., mixturesof formaldehyde and methylol compounds such, for instance, as dimethylolurea, trimethylol melamine, hexarnethylol mel- 1 amine, etc. s

The ratio of the aldehydic reactant to the triazine derivative may bevariedover a wide range depending upon the-particular starting reactantsemployed and the particular properties desired in the finished product.Ordinarily these reactants 20 are employed-in an amount. correspondingto at last one mol of the aldehyde, specifically formaldehyde,for eachmol of the triazine derivative.

Thus, we may use, for example, from 1 to or or more mols of an aldehydefor each mol of the triazine derivative. When. the. aldehyde isavailable for reaction in the form of an alkylol tive such, forinstance, as dimethylol urea, trimethylol melamine, etc., then higheramounts of 'such'aldehyde-addition products are used, for

instance from 2 or 3 up to or or more mols of such alkylol derivativesfor each mol of the triazine derivative.

As indicated hereinbefore, and as further 35 shown by a number of theexamples, the properties of the fundamental resins of this inventionmaybe varied widely by introducing other modifying bodies before, duringor after effecting condensation between the primary components. 40 Thus,as modifying agents we may use, for example, methyl, ethyl, propyl,isopropyl, isobutyl,

hexyl, etc.,- alcohols; polyhydric 'alcohols such, I

for example, as diethylene glycol, triethylene glycol, pentaerythritol,etc.; alcohol-ethers, e. g., ethylene glycol monomethylether, ethyleneglycol monoethylether, ethyleneglycol mono- 'butyl ether, diethyleneglycol monomethyl ether, diethylene glycol monoethylether, diethyleneglycol monobutyl'ether, etc.; amides, e. g., formamide, stearamide,acrylamide, benzene sulfonamides, toluene sulfonamides, adipic diamide,phthalamide, etc.; amines, e. g., ethylene diamine, phenylene diamine,etc.; ketones, includ' .ing halogenated ketones, etc.; nitriles,includinghalogenated nitriles, e. g., succinonitrile, acrylo nitrile,chloroacetonitriles, etc.; acylated ureas, more particularly halogenatedacylated ureas of.

the kind described, for example, in DAlelio Pat- The modifying bodiesalso may take the form of high molecular weight bodieswith or withoutresinous characteristics, for example hydrolyzed -wood products,formalized cellulose derivatives,

lignin, protein-aldehyde condensation products,

aminotriazole-aldehyde condensation products, melamine-aldehydecondensation products, etc.

Other examples of modifying bodies are the ureaaldehyde condensationproducts, the 'anilinealdehyde condensation products, phenol-aldehydecondensation products, modified or unmodiiled, saturated or unsaturatedpolyhydric alcohol-polycarboxylic acid condensation products,water-soluble cellulose derivatives, natural gums (l and resins such asshellac, rosin, etc.; polyvinyl and aldehyde-addition products may beused,

derivative, more particularly a methylol derivaent No. 2,281,559, issuedMay 5, 1942; and others.

aminodiazine-aldehyde condensation products,

compounds such as polyvinyl esters, e. g.', polyvinyl acetate, polyvinylbutyrate, etc., polyvinyl ethers, including polyvinyl acetals,specifically polyvinyl formal, etc.

Instead of efiecting reaction between a triazine derivative of the kindembraced by Formula I and an aldehyde, specifically formaldehyde, we maycause an aldehyde to condense with a salt (organic or inorganic) of thetriazine derivative or with a mixture of the triazine derivative and asalt thereof. Examples of organic and inorganic acids that may be usedin the preparation of such salts are hydrochloric, sulfuric,phosphoric,- borlc, acetic, chloroacetic, 'propionic, butyric, valeric,acrylic, oxalic, polyacrylic m ethacrylic, polymethacrylic, malonic,succinic, adipic, maleic, fumaric, malic, benzoic, salicylic, phthalic,camphoric, etc. b Dyes, pigments, plasticizers, mold lubricants,opacifiers and various fillers, (e. g., wood fiour, glass fibers,asbestos, including defibrated asbestos, mineral wool, mica, clothcuttings, etc.) may be compounded with the resin in accordance withconventional practice to provide various thermoplastic ,andthermosetting molding com-- positions.

The modified and unmodified resinous compositions of this invention havea wide variety of uses. For example. in. addition to their use in theproduction of molding compositions, they may be used as modifiers ofother natural and synthetic resins, as laminating varnishes in theproduction of laminated articlm wherein sheet materials, e. g., paper,cloth, sheet asbestos, plywood, etc., are coated and impregnated withthe resin, superimposed and thereafter united under heat and pressure.They may be used in the production of wire or baking enamels from whichinsulated wires and other coated products are made, for bonding orcementing together mica flakes to forin a laminated mica article, for

bonding together abrasive grains in the production of resin-bonded'a'brasive'articles such, for instance, as grindstones, sandpapers,etc.', in the manufacture of electrical resistors, etc. They also may beemployed for treating cotton, linen and other cellulosic materials insheet or other form. They also may beused as impregnants for electricalcoils and for other electrically insulating applications.

What we claim as new and desire to secure by Letters Patent of theUnited States is:

1. .A composition of matter comprising. the

' product of reaction of ingredients comprising an aldehyde and acompound corresponding to the 1 general formula and halo-hydrocarbonradicals, Y represents a polyacyl radical of a polycarbo'xylic acid,"said I polyacyl radical being, a member of the class con"- slsting ofpolyacyl radicals of a polycarbo y ic acid wherein the acyl groups areattached di rectly to eachother, polyacyl radicals or a polycarboxylicacid wherein the acyl it f tached directly to a hydrocarbon radical. 4

product of reaction of ingredients comprising formaldehyde and acompound corresponding to the general formula where R represents amember of the class consisting of hydrogen and monovalent hydrocarbonand halo-hydrocarbon radicals, Y represents a polyacyi radical, of apolycarboxylic'acid, said polyacyl radical being a member of the classconsisting. of p'olyacyl radicals of a polycarboxylic acid wherein theacyl groups are attached directly to each other, olyacyl radicals of apolycarboxylic acid wherein the acyl groups are at-' tached directly toa hydrocarbon radical, and.

polyacyl radicals of a polycarboxylic acid wherein the acyl groups areattached directly to a halo-hydrocarbon radical, and n represents aninteger-having a value equal to the valency of the polyacyl radical ofY, i a

3. A composition of matter comprising the product of reactionofingredients comprising an 3 aldehyde and acompound corresponding to thegeneral formula N/ N I Y n-Ne rinwhere Y represents a polyacyl radicalof. an unr substituted aliphatic polycarboxylic acid and n represents aninteger having'a value equal valency oi the polyacyl radical of Y.

4. A composition of matter comprising the aldehyde and a compoundcorresponding to the general formula Y BINT- /(IJ-NHNH- where Yrepresents a polyacyl radical oi an unsubstituted aromaticpolycarboxylic acid and n reprgents an integer having a value equal tothe u valency of the polyacyl radical of Y,

8. A composition as in claim 1 wherein the reaction product is theproductobtained by eiIect-' ing initial reaction between the statedcomponents under alkaline conditions.

7 A composition as in claim 1 wherein the reaction product is analcohol-modified reaction product of the stated components. I "'(.,;2@'heat-curable resinous composition coin- -heat-convertiblecondensationproduct of ingredients comprisingformaldehyde and product of reaction ofingredients comprising an carbonyl).

13. A composition comprising the resinous condensation product ofingredients comprising an aldehyde and a bis-(di'amino s-triazir'iylhydrazinocarbonyl) benzene.

14. A composition comprising the product of reaction of ingredientscomprising a urea, an aldehyde and a compound corresponding to thegeneral formula NHR where R represents a member of the class consistingof hydrogen and monova'lent hydrocarbon and halo-hydrocarbon radicals, Yrepresents a polyacyl radical of a polycarboxylic acid, said polyacylradical being a member of the class consisting of polyacyl radicals of apolycarboxylic acid wherein the acyl' groups are attached direct ly toeach other-,polyacyl radicals of a polycarboxylic acid wherein the acylgroups are attached directly to a hydrocarbon radical, and polyacylradicals of a polycarboxylic acid wherein the acyl' 8 2,338,404 acompound corresponding to the general urea. formaldehyde and a compoundcorrespond formula ing to the general formula l I 1H: NH:

N/ N 'Y N/ \N Y ii mN- NH NH- mN- --NHNH- N n I i I N I n v I where Yrepresents a polyacyl radical of a polywhere Y represents apolyacylradical of a polycarboxylic acid, said polyacyl radical being acarboxync acid 594d po y cyl radical being a member of the classconsisting of polyacyl radimember of the class coPslstmg of W- cals of apolycarboxylm a wherein acyl cals 91' a polycarboxylic acid wherein theacyl groups are attached directly to each other, polygroups are attachedd e to each Q acyl radicals of. a polycarboxylic acid wherein 15 Wradical? P 9 acld wherein the acyl groups are attached directly to a theacyl groups are attached directly to a hydrocarbon radical, and polyacylradicals of a poly-- carbon radical d polyacyl radicals of polycarboxylic acid wherein the acyl grou are .carboxylic acid wherein theacyl groups are at-. tached directly to a halo-hydrocarbon radical,mched directly to ham'hydIPmrmn radical and n represents an integerhaving a value equal 2 and n represents an integer haYmg Value equaltothe valency of the polyacyl radical of Y. to the valency the polyacylradical of I 8. A product comprising the cured resinous 16. Acomposition comprising the resinous composition of claim product of1reaction of ingredients contgri'ising 9. A composition of mattercomprising the urea" 9 dehyde, and resinous condensation product ofingredients g' hydrazmocairgonyl) i th comprising an aldehyde and abis-(diamino s- A resinous compos t on compnsmg e triazmyl.hydrazmocarbonyl) alkana product of reaction of ingredients comprisingdi- 10. A composition of matter comprising the methyl ureaaud bls'miammos'mazlnyl resinous condensation product of ingredients q g'g g zggggg iggih the product of comprising an aldehyde and alpha' beta-bis-(dii r a sf in r dients com g lamina an amino s-triazinyl hydrazinocarbonyl)ethane e on o g e p 8 me 11 A resinous composition comprising thealdehyde 1 compnund correspondingto the product of reaction ofingredients comprising general form a I I formaldehyde and .alpha,beta-bis-(diamino s-. NHR triazinyl hydrazinocarbonyl) ethane.

- 12. A composition comprising the resinous con- II I densation productof ingredients comprising an RHNAE J aldehyde and bis-(diaminos-triazinyl hydrazino- 40 where/B represents a member of theclass-consisting of hydrogen and monovalent hydrocarbon andhalo-hydrocarbon radicals, Y represent apolyacyl radical of apolycarboxylic acid, said polyacyl radical being a member of the classconsisting ot'polyacyl radicals of a polycarboxylic acid wherein thea'cyl groups are attached directly to each other, polyacyl radicals of apolycarboxylic acid whereinthe acylgroups are attached directly'to ahydrocarbon radical, and polyacyl radicals or a polycarboxylic acidwherein the acyl groups are attached directly to a halo-hydrocarbonradical, and n represents an integer' having a value equal to thevalency of the polyacyl radicai 19.. A heat curable compositioncomprising the heat-convertible resinous reaction product of (1) apartial condensation product of ingredients comprising formaldehyde anda compound corre- I spending to the general formula acyl groups areattached directly to a hydrocarrepresents an integer having a valueequal to the valency of the polyacyl radical of Y, and (2) a curingreactant.

20. The method of preparing new synthetic composition which compriseseffecting reaction between ingredients comprising an aldehyde and acompound corresponding to the general formula 10 where R represents amember or the class consisting of hydrogen and monovalent hydrocarbonand halo-hydrocarbon radicals, Y represents a polyacyl radical of apblycarboxylic acid, said polyacyl radical being a member of the classconsisting o1 polyacyl radicals of a polycarboxylic acid wherein theacyl groups are attached direct- 1y to each other; polyacyl radicals ofa polycarboxylic acid wherein the acyl groups are attached directly to ahydrocarbon radical, and polyacyl' radicals of a polycarboxylic acidwherein the acyl groups are attached directly to a halo-hydrocarbonradical, and n represents an integer having a value equal to the valencyof the polyacyl radical 15 of Y.

.GAETANO F. DALELIO. JAMES W. UNDERWOOD.

CERTIFICATE OF CORRECTION. I Patent No. 2,55 A9h. Janua L 191m.

GAETANO IF. DIALELIO, ET AL.

It is hgr eby certified that error appears in the printed sptcificationof the above 'numbered patent requiring 'corr'ectionas follows: Page 1,first column, 1111558 59, for "tert'ir.ry-" read tertiarypag 5, firstcolumn, line 50, for "preenec" r'ead --presence--; line 59, for"D'Aleio" read -D A1e lio--.; page first column, lirie LL1, for- "t9"read --at--;'

same page,- sbc'ond column, 1ine 66, and ipage 5', first column, line ,for "ch1o1 -a etmqide" re ad ch1o roacetgm 1de--; 'pfige 5, secbnd.column, line 68, for "polylirihyl" I ead --polyv1ny1-;"1 ag e 6, firstcoluinn, l'ine 2 6, for "111" 'rad -of-rjand that the said'Letters IPatent should-be read with this cbrrecuon -thereingthat the sanen 1ayconom to the record of the case in the Patent'office j, Q I Signed and;sealed thigllth day of, 'Apr11' 'A- D. 19th.. I

. v V 1.9511; Frazbzf Y (Seal) Act'ihg. qpmlmigs sib er 0:1: Patents.

